CN114436732A - Method and system for preparing ethylbenzene and hydrogen by using refinery dry gas - Google Patents
Method and system for preparing ethylbenzene and hydrogen by using refinery dry gas Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 187
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 60
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000005336 cracking Methods 0.000 claims abstract description 62
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000005977 Ethylene Substances 0.000 claims abstract description 55
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 46
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 43
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 12
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 51
- 238000005406 washing Methods 0.000 claims description 51
- 238000011084 recovery Methods 0.000 claims description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 26
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 21
- 230000029936 alkylation Effects 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000000295 fuel oil Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 27
- 239000000446 fuel Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 28
- 239000007795 chemical reaction product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 239000002737 fuel gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- Chemical & Material Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of oil refining and chemical engineering, and discloses a method and a system for preparing ethylbenzene and hydrogen by using refinery dry gas, wherein (1) ethane-rich gas and/or alkane-rich refinery dry gas are cracked to obtain cracked gas containing ethylene and hydrogen; (2) recovering the carbon two component in the cracking gas; (3) selectively hydrogenating the recovered carbon two components to remove alkyne and/or dialkene in the carbon two components; (4) the hydrogenation product is contacted with benzene to carry out alkylation reaction independently or together with the ethylene-rich refinery dry gas to obtain ethylbenzene; (5) and (3) carrying out carbon-two concentration on the gas-phase material which does not participate in the alkylation reaction in the step (4) alone or together with the alkane-rich refinery dry gas to obtain ethane-rich gas and hydrogen-rich gas, and optionally, returning the obtained ethane-rich gas to the step (1) for cracking. The method can fully utilize the carbon-carbon second resource in the refinery dry gas, improve the utilization rate of ethane, improve the yield of ethylbenzene and hydrogen, and provide an effective way for fuel type oil refining enterprises to realize chemical transformation.
Description
Technical Field
The invention relates to the field of oil refining and chemical engineering, in particular to a method and a system for preparing ethylbenzene and hydrogen by using refinery dry gas.
Background
The refining integration has the functions of utilizing crude oil resources to the maximum extent, comprehensively utilizing byproducts and intermediate products, optimizing and configuring public works, reducing production and construction costs, giving full play to scale benefits, enhancing the risk resistance of enterprises and improving the profitability of the enterprises, and is a long-standing development strategy in the refining industry at home and abroad.
At present, the oil refining capacity is totally surplus, the demand of ethylene and downstream derivatives thereof is continuously increased, and the market gap of high-end petrochemical products is large. The conversion from fuel type to fuel-chemical type in refineries is a great trend of sustainable development of the oil refining industry, and the depth and the breadth of the integration of refining in the future are changed significantly. From the aspect of processing depth, the catalytic cracking device develops from the production of gasoline and diesel fuel to the deep catalytic cracking method for producing more low-carbon olefins, and has the advantages of strong raw material adaptability, flexible processing scheme, high liquid product yield, good product quality and the like, and the development of the oil refining device to the low-carbon olefins needs to fully consider and utilize a plurality of saturated hydrocarbon resources produced by a refinery.
A large amount of dry gas can be generated in the oil refining production process, wherein some dry gas, such as the dry gas generated in the production processes of catalytic cracking, thermal cracking, delayed coking, hydrocracking and the like, contains a plurality of components of carbon and carbon, and has high recovery value, but the large amount of dry gas is burnt as fuel at present to cause resource waste.
At present, the utilization modes of refinery dry gas mainly comprise two modes, one mode is to use catalytic dry gas as raw material of an ethylbenzene/styrene device, but the method only utilizes ethylene, ethane and other components in the dry gas to be still used as fuel gas for burning. The other dry gas utilization mode is to recover carbon and the above components in the dry gas and send the recovered components to an ethylene device as raw materials, and the methods for recovering ethane and ethylene components from the dry gas which are industrialized at present mainly comprise a cryogenic separation method, a pressure swing adsorption method and a shallow cold oil absorption method, and are not suitable for fuel type oil refining enterprises without matched ethylene devices.
In conclusion, the ethane resource in the dry gas of the fuel type oil refining enterprises is lack of effective utilization means.
Disclosure of Invention
The invention aims to overcome the problem that the carbon in the dry gas of the fuel type oil refining enterprise is lack of effective utilization in the prior art, and provides a method and a system for preparing ethylbenzene and hydrogen by using the refinery dry gas.
In order to achieve the above objects, one aspect of the present invention provides a method for preparing ethylbenzene and hydrogen using refinery dry gas, the method comprising:
(1) cracking: cracking the ethane-rich gas and/or the alkane-rich refinery dry gas to obtain cracked gas containing ethylene and hydrogen;
(2) and (3) recovering carbon: recovering the carbon two component in the cracking gas;
(3) hydrogenation: selectively hydrogenating the recovered carbon two components to remove alkyne and/or dialkene in the carbon two components;
(4) alkylation: under the condition of alkylation reaction, the hydrogenation product is contacted with benzene alone or together with refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(5) and (3) carbon concentration: and (3) carrying out carbon-two concentration on the gas-phase material which does not participate in the alkylation reaction in the step (4) alone or together with the dry gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally returning the obtained ethane-rich gas to the step (1) for cracking.
The invention provides a system for preparing ethylbenzene and hydrogen by using refinery dry gas, which comprises the following units connected in sequence:
(S1) cleavage unit: cracking the ethane-rich gas and/or the alkane-rich refinery dry gas to obtain cracked gas containing ethylene and hydrogen;
(S2) a carbon two recovery unit: used for recovering the carbon two components in the cracking gas obtained by the cracking unit;
(S3) a hydrogenation unit: the selective hydrogenation is carried out on the carbon two components recovered by the carbon two recovery unit to remove alkyne and/or dialkene in the carbon two components;
(S4) alkylation unit: the catalyst is used for enabling the hydrogenation product to be in contact with benzene alone or together with the refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(S5) a carbon two concentration unit: the device is used for carrying out carbon-two concentration on gas-phase materials which do not participate in alkylation reaction in the alkylation unit alone or together with dry refinery gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally, the carbon-two concentration unit is connected with the cracking unit so that the ethane-rich gas obtained by the carbon-two concentration unit can be returned to the cracking unit for cracking.
The technical scheme adopted by the invention has the following advantages:
(1) the technical scheme of the invention realizes the transformation of oil refining to chemical industry in a simple mode, fully utilizes ethane resources in refinery dry gas, increases the yield of ethylbenzene and hydrogen, and has simple process and small investment;
(2) in a preferred embodiment, the invention can fully utilize the prior oil refining device to separate and treat the cracking gas, thereby saving the equipment investment;
(3) in a preferred embodiment, the technical scheme of the invention can be deeply supported by an oil refining device, a cracking gas-oil washing tower adopts heavy oil washing from the oil refining device, and washing liquid is sent to the oil refining device for treatment; heavy components extracted from the light cold benzene washing part can be sent to a reforming device for treatment. On one hand, the investment of the device is saved, and on the other hand, the energy consumption of the device is reduced;
(4) in a preferred embodiment, the technical scheme of the invention can be mutually coupled with the existing oil refining device, and can supply heat to oil products of the oil refining device by using the high temperature of the pyrolysis gas, thereby being more beneficial to the comprehensive utilization of energy;
(5) under the condition that the dry gas treatment capacity of a refinery is not large, the cracking furnace can adopt an electric heating mode, no flue gas is discharged, and meanwhile, the heat of the flue gas is not required to be recovered, so that the investment is reduced.
Drawings
FIG. 1 is a schematic diagram of a system for producing ethylbenzene and hydrogen from refinery dry gas;
FIG. 2 is a schematic diagram of the process for making ethylbenzene and hydrogen using refinery dry gas of example 1;
FIG. 3 is a schematic of the process for making ethylbenzene and hydrogen using refinery dry gas of example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In a first aspect, the present invention provides a process for producing ethylbenzene and hydrogen from refinery dry gas, the process comprising:
(1) cracking: cracking ethane-rich gas and/or dry refinery gas rich in alkane (especially ethane) to obtain cracked gas containing ethylene and hydrogen;
(2) and (3) recovering carbon dioxide: recovering the carbon two component in the cracking gas;
(3) hydrogenation: selectively hydrogenating the recovered carbon two components to remove alkyne and/or dialkene in the carbon two components;
(4) alkylation: under the condition of alkylation reaction, the hydrogenation product is contacted with benzene alone or together with refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(5) and (3) carbon concentration: and (3) carrying out carbon-two concentration on the gas-phase material which does not participate in the alkylation reaction in the step (4) alone or together with the dry gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally returning the obtained ethane-rich gas to the step (1) for cracking.
In the present invention, the refinery dry gas contains ethane and/or ethylene.
According to one embodiment of the invention, when the refinery dry gas is rich in ethane, the refinery dry gas is added from step (1) and/or step (5).
According to one embodiment of the invention, the refinery dry gas is added from step (4) when the refinery dry gas is rich in ethylene.
According to one embodiment of the invention, when the refinery dry gas is rich in ethane and ethylene, the refinery dry gas is added from at least one of step (1), step (4) and step (5).
In the present invention, preferably, the method further comprises: (6) hydrogen extraction: hydrogen is separated from the hydrogen-rich component.
In the present invention, in the step (3), preferably, the method further comprises: and (3) absorbing heavy components in the obtained hydrogenation product by using aromatic hydrocarbon. The preferred embodiment is more beneficial to removing heavy components, impurities and the like in the obtained hydrogenation product.
More preferably, the aromatic hydrocarbon is selected from a benzene series having 6 to 10 carbon atoms, preferably from at least one of benzene, ethylbenzene, toluene and xylene, and more preferably from benzene. In the case that the absorbent is preferably selected from benzene, the reaction heat generated by the hydrogenation reaction can vaporize part of the benzene, thereby reducing the energy consumption of the benzene vaporization in the ethylbenzene/styrene device, fully utilizing the reaction heat and not introducing other impurities into the gas phase of the hydrogenation product.
In the present invention, the purpose of cracking ethane is to crack the ethane to generate high-value-added olefin products such as ethylene (for example, cracking to generate ethylene, propylene, etc.), and the cracking manner and conditions are not particularly required, and may be selected conventionally in the art as long as the ethane can be cracked to generate ethylene.
In the invention, the refinery dry gas can be dry gas generated in the production processes of catalytic cracking, thermal cracking, delayed coking, hydrocracking and the like, and contains three components of carbon and carbon. As previously mentioned, depending on the composition of the refinery dry gas, it can be introduced at different stages to maximize the use of the dry gas.
In the present invention, the cracked gas obtained by cracking has a relatively high temperature and contains heavy components with carbon atoms of more than 8, and in order to effectively recover the heat of the cracked gas and the heavy components in the cracked gas and further reduce the temperature of the cracked gas, preferably, the method further comprises: and (3) carrying out oil washing and cooling on the pyrolysis gas containing ethylene and hydrogen, and then carrying out carbon dioxide recovery on the pyrolysis gas subjected to oil washing and cooling. The preferred method can save a water washing tower and a dilution steam generation system in the traditional separation process of the ethane cracking gas, can further cool the cracking gas after oil washing by using a water cooler, not only saves investment, but also reduces the coking tendency of the oil washing tower by returning the oil used for oil washing to an oil refining device for processing after recovering heat and heavy components, and solves the emulsification problem of the water washing tower in the traditional separation process.
In the present invention, the temperature of the cracked gas after oil washing and cooling is preferably about 40 ℃, for example, 35 to 45 ℃.
In the invention, the oil used in the oil washing is preferably heavy oil with a distillation range of more than or equal to 150 ℃, more preferably heavy oil with a distillation range of 150 ℃ to 450 ℃, and even more preferably heavy oil with a distillation range of 200 ℃ to 350 ℃.
More preferably, the heavy oil of the oil refinery is used as an absorbent to absorb the heat of the cracked gas and heavy components in the cracked gas and then return the cracked gas to the oil refinery for processing.
In the invention, the method for recovering the carbon two can recover the carbon two by independently arranging a carbon two recovery unit or entering the existing oil refining device gas compressor, absorption-stabilization system and the like for catalytic cracking, delayed coking and the like, and produce the ethylene-rich gas by alkali washing and desulfurization.
Preferably, the separately arranged carbon dioxide separation unit is preferably a self-freezing separation process, a rectification separation process, or a light cold benzene washing process, preferably a light cold benzene washing process. Preferably, the absorbent used in the light cold benzene washing process is selected from benzene series with 6-10 carbon atoms, such as benzene, ethylbenzene, toluene, xylene, etc. The light cold benzene washing process is adopted to recover and separate the carbon two to obtain the carbon two component and the absorbent (rich solvent) after absorbing the carbon three or more components.
Preferably, the conditions of the benzene absorption column in the light cold benzene wash process include: the temperature is 10-60 ℃, the pressure is 0.5-4MPa, and the theoretical plate number is 10-60.
In the invention, the shallow cold benzene washing process further comprises the step of pretreating the pyrolysis gas obtained in the step (1), preferably, the shallow cold benzene washing process further comprises the step of compressing and/or cooling the pyrolysis gas obtained in the step (1) so as to compress and/or cool components such as hydrogen, carbon one to carbon six hydrocarbons, water, carbon monoxide, carbon dioxide, hydrogen sulfide and the like in the pyrolysis gas, and then the components are contacted with an absorbent in the shallow cold benzene washing process so as to improve the recovery effect of carbon two. More preferably, the process further comprises compressing the cracked gas to a pressure of 2-5MPa and/or cooling to a temperature of 0-40 ℃. In the present invention, all the pressures are gauge pressures unless otherwise specified. In order to avoid excessive temperature during the compression, the compression may be segmented, preferably two to five or two to six segments.
In a preferred embodiment of the invention, the mass content of the non-aromatic hydrocarbon compounds with more than five carbon atoms in the carbon two-component separated by adopting a shallow cold benzene washing process is less than 0.1 percent, the molar content of the butylene is less than 5ppm, and the molar content of the propylene is less than 300 ppm; preferably, the molar content of propylene is less than 10 ppm.
According to the light cold benzene washing process adopted in the invention, the method further comprises the step of stripping the absorbent (rich solvent) contacted with the pyrolysis gas to separate carbon and the following components, and the stripping conditions are not particularly limited as long as the carbon and the following components in the rich solvent can be separated to form a gas phase material containing carbon-one and carbon-two hydrocarbons and a rich solvent liquid phase material containing more than carbon-three hydrocarbons. Preferably, the stripping conditions at least satisfy: the theoretical plate number is 10-60 and the pressure is 0.1-3 MPa. In addition, the loss of ethylene is controlled by controlling the carbon dioxide or the molar content of ethylene in the tower bottom in the stripping process.
In the present invention, in order to further improve the recovery rate of the carbon two component, preferably, the method further comprises: compressing and cooling the cracked gas obtained in the step (1), wherein the method further comprises the following steps: the carbon and the following components separated from the rich solvent are returned to the compressor section.
In the present invention, the hydrogenation is a hydrogenation reaction, and in order to improve the effect of selective hydrogenation to effectively remove alkynes and/or dienes from the carbon dioxide component, a person skilled in the art can select the hydrogenation conditions according to actual requirements and the kind of the catalyst, which is not described herein again.
It is to be understood that the hydrogenation needs to be carried out in the presence of a catalyst, and the present invention is not particularly limited to the kind of the catalyst, and may be a catalyst conventionally used in the art, such as a hydrogenation catalyst disclosed in CN107970927A, CN102408916A or CN 101451077A.
In the present invention, the alkylation reaction conditions are not particularly limited as long as ethylene and benzene can react to produce ethylbenzene, and thus, the details thereof are not repeated herein.
In the present invention, the method of the carbon two-concentration is not particularly limited, and preferably, the method of the carbon two-concentration is a pressure swing adsorption method and/or a shallow cold oil absorption method.
In the present invention, the pressure swing adsorption conditions are not particularly limited, and may be those conventionally used in the art, as long as the ethane-rich gas and the hydrogen-rich component can be further separated from the gas phase feed that has not participated in the alkylation reaction. Wherein the hydrogen-rich component also contains methane.
In the present invention, the conditions of the shallow cold oil absorption process are not particularly limited, and may be those conventionally used in the art, as long as the ethane-rich gas and the hydrogen-rich component can be further separated from the gas phase feed that does not participate in the alkylation reaction.
In the present invention, in order to further improve the utilization rate of ethane and the production of ethylbenzene and hydrogen, preferably, the method further comprises: the ethane-rich gas obtained from the carbon dioxide concentration is recycled to step (1) for cracking either alone or together with the alkane-rich refinery dry gas.
In a second aspect, the present invention provides a system for preparing ethylbenzene and hydrogen by using refinery dry gas, as shown in fig. 1, the system comprises the following units connected in sequence:
(S1) cleavage unit: cracking the ethane-rich gas and/or the alkane-rich refinery dry gas to obtain cracked gas containing ethylene and hydrogen;
(S2) a carbon two recovery unit: used for recovering the carbon two components in the cracking gas obtained by the cracking unit;
(S3) a hydrogenation unit: the selective hydrogenation is carried out on the carbon two components recovered by the carbon two recovery unit to remove alkyne and/or dialkene in the carbon two components;
(S4) alkylation unit: the catalyst is used for enabling the hydrogenation product to be in contact with benzene alone or together with the refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(S5) a carbon two concentration unit: the device is used for carrying out carbon-two concentration on gas-phase materials which do not participate in alkylation reaction in the alkylation unit alone or together with dry refinery gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally, the carbon-two concentration unit is connected with the cracking unit so that the ethane-rich gas obtained by the carbon-two concentration unit can be returned to the cracking unit for cracking.
In the present invention, the refinery dry gas contains ethane and/or ethylene.
According to one embodiment of the invention, when the refinery dry gas is rich in ethane, the refinery dry gas is added from (S1) and/or (S5).
According to one embodiment of the invention, the refinery dry gas is added from (S4) when the refinery dry gas is rich in ethylene.
According to an embodiment of the present invention, when the refinery dry gas is rich in ethane and ethylene, the refinery dry gas is added from at least one of (S1), (S4) and (S5).
In the present invention, preferably, the system further includes: (S6) hydrogen extraction unit: and the obtained hydrogen-rich component is subjected to a hydrogen extraction unit to obtain a hydrogen product.
In the present invention, it is preferable that the system further comprises an absorption column for absorbing and removing heavy components in the hydrogenation product obtained in (S3). More preferably, the heavies-removed hydrogenated product withdrawn overhead from the absorber is sent to an alkylation unit.
In the present invention, the heating method of the cracking unit (cracking furnace) may be fuel gas heating or electric heating. Under the condition that the dry gas treatment capacity of a refinery is not large, the cracking furnace can adopt an electric heating mode, no flue gas is discharged, and meanwhile, the heat of the flue gas is not required to be recovered, so that the investment is reduced.
In the present invention, it is preferable that the cracked gas obtained in (S1) is first cooled in a waste boiler to generate steam, and then subjected to oil washing and cooling, and then sent to carbon recovery.
More preferably, the system is connected with the oil refining plant, so that heavy oil from the oil refining plant can be used for absorbing heavy components in the cracked gas, and the heavy oil after absorbing heat and the heavy components is returned to the oil refining plant for processing.
In the invention, (S2), a carbon dioxide recovery unit can be independently arranged, and the carbon dioxide can also enter the existing oil refining device gas compressor and absorption-stabilization system for catalytic cracking, delayed coking and the like to recover carbon dioxide, and the ethylene-rich gas is produced through alkali washing and desulfurization. The independently arranged carbon dioxide separation unit can adopt a freezing and rectifying separation process or a light cold benzene washing process; preferably, the absorbent and conditions used in the light cold benzene wash process are as described above.
In the present invention, the system further preferably includes: the oil washing tower and the cooler are used for carrying out oil washing and cooling on the cracking gas containing ethylene and hydrogen and then sending the cracking gas into the carbon dioxide recovery unit. In a preferred embodiment of the invention, cracking gas is directly sent to a catalytic cracking unit gas compressor and an absorption-stabilization system for treatment after being washed with oil and cooled, and then is subjected to alkaline washing for desulfurization, and then is sent to a subsequent hydrogenation unit.
In the present invention, preferably, the hydrogenation unit in (S3) comprises a hydrogenation reactor.
More preferably, the carbon dioxide component of (S3) is dried prior to entering the hydrogenation reactor.
In the present invention, preferably, (S5) the carbon-dioxide concentration unit includes a pressure swing adsorption device and/or a shallow cold oil absorption device, more preferably a pressure swing adsorption device. (S5) the hydrogen-rich component contains hydrogen, nitrogen, methane and the like.
In the present invention, preferably, (S6) the hydrogen product and the methane-rich product are obtained from the hydrogen extraction unit, and the methane-rich product can be directly sent to the cracking furnace of the present apparatus to be used as fuel gas for the cracking furnace.
According to a particularly preferred embodiment of the invention, the method comprises the following steps:
(a) sending the ethane-rich gas into an ethane cracking unit for cracking, washing the obtained cracked gas in an oil washing tower, carrying out oil washing on the cracked gas through wax oil (with the distillation range of 250-;
(b) sending the compressed and cooled pyrolysis gas into a carbon dioxide recovery unit, and recovering a carbon dioxide component in a benzene absorption tower by adopting a shallow cold benzene washing process; the benzene absorption tower conditions in the light cold benzene washing process comprise: the temperature is 20-40 ℃, the pressure is 3-3.4MPa, and the theoretical plate number is 38-42;
(c) selectively hydrogenating the recovered carbon dioxide component to remove alkyne and dialkene to obtain a hydrogenation product, absorbing more than three heavy components of carbon in the obtained hydrogenation product by adopting benzene, and feeding the hydrogenation product absorbing the heavy components and catalytic dry gas containing ethylene into an alkylation unit;
(d) performing alkylation reaction on ethylene and benzene in the catalytic dry gas and the carbon two-component in an alkylation unit to generate a reaction product containing ethylbenzene, extracting the ethylbenzene in the obtained reaction product in a liquid form, and feeding the rest reaction product into a carbon two-component concentration unit in a gas phase form;
(e) adopting a pressure swing adsorption device (PSA) or a shallow cold oil washing method to perform carbon dioxide concentration on the residual reaction product in the step (d) alone or together with ethane-containing refinery dry gas to obtain ethane-rich gas and hydrogen-rich components, and returning the ethane-rich gas to an ethane cracking unit;
(f) sending the hydrogen-rich gas component obtained in (e) to a hydrogen extraction unit to obtain a hydrogen product and a methane product.
The present invention will be described in detail below by way of examples. In the following examples, the hydrogenation catalyst used was catalyst LC-3 prepared in example 3 disclosed in CN 107970927A.
Example 1
(1) Sending ethane-rich gas into an ethane cracking unit for cracking by adopting the process shown in figure 2, washing the obtained cracked gas in an oil washing tower, absorbing heavy components and partial heat of the cracked gas by wax oil (with the distillation range of 275 ℃) in the oil washing tower, sending the cracked gas into a water cooler for cooling to 40 ℃, and then compressing to increase the pressure of the cracked gas to 3.5MPa to obtain the compressed and cooled cracked gas;
(2) sending the compressed and cooled cracking gas into a carbon dioxide recovery unit, recovering a carbon dioxide component in a benzene absorption tower by adopting a shallow cold benzene washing process, and separating the carbon dioxide component in the benzene absorption tower; the ethylene amount entering the carbon two recovery unit, the ethylene amount recovered by the carbon two recovery unit and the ethylene recovery rate are shown in table 3; the benzene absorption tower conditions in the light cold benzene washing process comprise: the temperature is 30 ℃, the pressure is 3.2MPa, and the theoretical plate number is 40;
(3) in the presence of a hydrogenation catalyst, selectively hydrogenating the recovered carbon two components to remove alkyne and dialkene to obtain a hydrogenation product, absorbing more than three carbon heavy components in the obtained hydrogenation product by adopting benzene, and sending the hydrogenation product absorbing the heavy components and catalytic dry gas of the components shown in the table 1 into an alkylation unit, wherein the treatment capacity of the catalytic dry gas is 16143 kg/h;
(4) the ethylene in the dry gas and the carbon two component is catalyzed in the alkylation unit to carry out alkylation reaction with benzene to generate a reaction product containing ethylbenzene, the ethylbenzene in the obtained reaction product is extracted in a liquid form, the ethylene amount and the ethylbenzene yield entering the alkylation reaction unit are shown in a table 3, and the rest reaction product enters the carbon two concentration unit in a gas phase form;
(5) removing light components such as hydrogen, methane, nitrogen, oxygen and the like in the residual reaction product by using a pressure swing adsorption device (PSA) to obtain ethane-rich gas, and returning the ethane-rich gas to the ethane cracking unit;
(6) and (3) sending the light components such as hydrogen, methane, nitrogen, oxygen and the like removed in the step (5) to a hydrogen extraction unit to obtain a hydrogen product and a methane product, wherein the obtained methane product can be used as fuel gas of a cracking device, and the yield of the hydrogen product is shown in Table 3.
Example 2
(1) Sending ethane-rich gas into an ethane cracking unit for cracking by adopting a process shown in figure 3, washing the obtained cracked gas in an oil washing tower, absorbing heavy components and partial heat of the cracked gas by wax oil (with the distillation range of 275 ℃) in the oil washing tower, sending the cracked gas into a water cooler for cooling to 40 ℃, and then compressing to increase the pressure of the cracked gas to 3.5MPa to obtain the compressed and cooled cracked gas;
(2) sending the compressed and cooled cracking gas into a catalytic cracking device (a carbon dioxide recovery unit) to separate a carbon dioxide component; the ethylene amount entering the carbon two recovery unit, the ethylene amount recovered by the carbon two recovery unit and the ethylene recovery rate are shown in table 3;
(3) in the presence of a hydrogenation catalyst, selectively hydrogenating the recovered carbon two components to remove alkyne and dialkene to obtain a hydrogenation product, absorbing more than three carbon heavy components in the obtained hydrogenation product by adopting benzene, and sending the hydrogenation product absorbing the heavy components and catalytic dry gas of the components shown in the table 1 into an alkylation unit, wherein the treatment capacity of the catalytic dry gas is 16143 kg/h;
(4) the ethylene in the dry gas and the carbon two component is catalyzed in the alkylation unit to carry out alkylation reaction with benzene to generate a reaction product containing ethylbenzene, the ethylbenzene in the obtained reaction product is extracted in a liquid form, the ethylene amount and the ethylbenzene yield entering the alkylation reaction unit are shown in a table 3, and the rest reaction product enters the carbon two concentration unit in a gas phase form;
(5) removing light components such as hydrogen, methane, nitrogen, oxygen and the like in the residual reaction product by using the reformed dry gas and the residual reactant obtained in the step (4) through a shallow cold oil washing method to obtain ethane-rich gas, and returning the ethane-rich gas to the ethane cracking unit; the treatment capacity of the reformed dry gas is 3403kg/h, and the composition is shown in Table 2;
(6) and (3) sending the light components such as hydrogen, methane, nitrogen, oxygen and the like removed in the step (5) to a hydrogen extraction unit to obtain a hydrogen product and a methane product, wherein the obtained methane product can be used as fuel gas of a catalytic cracking device, and the yield of the hydrogen product is shown in Table 3.
Comparative example 1
The dry gas feed was made at 16143kg/h with the specific composition shown in Table 1, and was passed through an ethylbenzene/styrene plant only, and the amounts of ethylbenzene and hydrogen obtained using this process are shown in Table 3.
TABLE 1
| Composition of | mol％ |
| Hydrogen gas | 27.50 |
| Nitrogen gas | 9.58 |
| Oxygen gas | 0.68 |
| CO | 0.39 |
| CO2 | 2.11 |
| Methane | 24.65 |
| Acetylene | 0.05 |
| Ethylene | 18.56 |
| Ethane (III) | 14.81 |
| Propylene (PA) | 0.90 |
| Propane | 0.26 |
| Isobutane | 0.16 |
| N-butane | 0.04 |
| Butene (butylene) | 0.04 |
| Isobutene | 0.04 |
| Trans-2-butene | 0.04 |
| Cis-2-butene | 0.03 |
| C5 | 0.16 |
TABLE 2
TABLE 3
| Example 1 | Example 2 | Comparative example 1 | |
| Ethylene amount (kg/h) of carbon inlet carbon recovery unit | 2056 | 2999 | - |
| Amount of ethylene recovered in the carbon two recovery Unit (kg/h) | 2055 | 2992 | - |
| The recovery rate of ethylene is% | 99.95 | 99.8 | - |
| Ethylene (kmol/h) | 190.4 | 223 | 117.4 |
| Ethylbenzene production (ten thousand tons/year) | 15.9 | 18.6 | 9.7 |
| Hydrogen production (Nm)3/h) | 6410.2 | 7972 | 4752 |
From the above results, it can be seen that the method of the present invention can effectively improve the yield of ethylbenzene and hydrogen, which can reach 15.9 ten thousand tons/year or more and 6400 Nm/year3More than h; the utilization rate of ethane and the recovery rate of ethylene in the carbon two recovery unit are improved (reaching more than 99.8%), the energy consumption is low, the process is simple, the operation and the control are easy, and an effective way can be provided for realizing chemical transformation of fuel type oil refining enterprises.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for preparing ethylbenzene and hydrogen by using refinery dry gas is characterized by comprising the following steps:
(1) cracking: cracking the ethane-rich gas and/or the alkane-rich refinery dry gas to obtain cracked gas containing ethylene and hydrogen;
(2) and (3) recovering carbon: recovering the carbon two component in the cracking gas;
(3) hydrogenation: selectively hydrogenating the recovered carbon two components to remove alkyne and/or dialkene in the carbon two components;
(4) alkylation: under the condition of alkylation reaction, the hydrogenation product is contacted with benzene alone or together with refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(5) and (3) carbon concentration: and (3) carrying out carbon-two concentration on the gas-phase material which does not participate in the alkylation reaction in the step (4) alone or together with the dry gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally returning the obtained ethane-rich gas to the step (1) for cracking.
2. The method of claim 1, wherein the method further comprises: (6) hydrogen extraction: hydrogen is separated from the hydrogen-rich component.
3. The method according to claim 1 or 2, wherein the method further comprises: heavy components in the obtained hydrogenation products are absorbed by aromatic hydrocarbon, and the hydrogenation products with the absorbed and removed heavy components are contacted with benzene alone or together with the ethylene-rich refinery dry gas.
4. The method according to any one of claims 1-3, wherein the method further comprises: and (3) carrying out oil washing and cooling on the pyrolysis gas containing ethylene and hydrogen, and then carrying out carbon dioxide recovery on the pyrolysis gas subjected to oil washing and cooling.
5. The process according to claim 4, wherein the oil used in the oil washing is a heavy oil, preferably a heavy oil with a distillation range of 150 ℃ or more, more preferably 150 ℃ and 450 ℃, and even more preferably 200 ℃ and 350 ℃.
6. The method according to any one of claims 1 to 5, wherein the method for carbon dioxide recovery is selected from a freeze separation process, a distillation separation process or a light cold benzene wash process, preferably a light cold benzene wash process;
preferably, the absorbent used in the light cold benzene washing process is selected from benzene series with 6-10 carbon atoms, and more preferably at least one of benzene, ethylbenzene, toluene and xylene;
and/or the conditions of the benzene absorption tower in the shallow cold benzene washing process comprise: the temperature is 10-60 ℃, the pressure is 0.5-4MPa, and the theoretical plate number is 10-60.
7. The process according to any one of claims 1 to 6, wherein the carbon two concentration process is a pressure swing adsorption process and/or a shallow cold oil absorption process.
8. A system for preparing ethylbenzene and hydrogen by using refinery dry gas is characterized by comprising the following units which are connected in sequence:
(S1) cleavage unit: cracking the ethane-rich gas and/or the alkane-rich refinery dry gas to obtain cracked gas containing ethylene and hydrogen;
(S2) a carbon two recovery unit: used for recovering the carbon two components in the cracking gas obtained by the cracking unit;
(S3) a hydrogenation unit: the selective hydrogenation is carried out on the carbon two components recovered by the carbon two recovery unit to remove alkyne and/or dialkene in the carbon two components;
(S4) alkylation unit: the catalyst is used for enabling the hydrogenation product to be in contact with benzene alone or together with the refinery dry gas rich in ethylene to carry out alkylation reaction to obtain ethylbenzene;
(S5) a carbon two concentration unit: the system is used for carrying out carbon-two concentration on gas-phase materials which do not participate in alkylation reaction in the alkylation unit alone or together with dry refinery gas rich in alkane to respectively obtain ethane-rich gas and hydrogen-rich components, and optionally, the carbon-two concentration unit is connected with the cracking unit so that the ethane-rich gas obtained by the carbon-two concentration unit can return to the cracking unit for cracking;
preferably, the system further comprises: (S6) hydrogen extraction unit: and the hydrogen-rich component obtained by the carbon two concentration unit is separated to obtain a hydrogen product.
9. The system of claim 8, further comprising an absorber column disposed between the hydrogenation unit and the alkylation unit for absorbing heavy components from the hydrogenated product for removal to the alkylation unit.
10. The system of claim 8 or 9, wherein the system further comprises: the oil washing tower and the cooler are used for carrying out oil washing and cooling on the pyrolysis gas containing ethylene and hydrogen;
and/or the carbon two concentration unit comprises a pressure swing adsorption device and/or a shallow cold oil absorption device, preferably a pressure swing adsorption device.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050277801A1 (en) * | 2004-06-11 | 2005-12-15 | Guangjin Chen | Combined process for recovering hydrogen, ethylene, ethane or separating ethylene cracked gas from dry gas of refinery plants |
| CN103772125A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by using refinery dry gas as raw material |
| CN103772126A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Combined method for preparing ethylbenzene by using refinery dry gas as raw material |
| CN111423301A (en) * | 2020-05-09 | 2020-07-17 | 中国石油化工股份有限公司 | Combined process for preparing ethylbenzene from refinery dry gas |
-
2020
- 2020-11-04 CN CN202011218246.8A patent/CN114436732A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050277801A1 (en) * | 2004-06-11 | 2005-12-15 | Guangjin Chen | Combined process for recovering hydrogen, ethylene, ethane or separating ethylene cracked gas from dry gas of refinery plants |
| CN103772125A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene by using refinery dry gas as raw material |
| CN103772126A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Combined method for preparing ethylbenzene by using refinery dry gas as raw material |
| CN111423301A (en) * | 2020-05-09 | 2020-07-17 | 中国石油化工股份有限公司 | Combined process for preparing ethylbenzene from refinery dry gas |
Non-Patent Citations (3)
| Title |
|---|
| 冷桂玲;田原宇;乔英云;史俊高;: "炼厂干气的综合应用技术", 天然气化工(C1化学与化工), no. 06, pages 71 - 75 * |
| 杨建华;: "齐鲁公司炼厂干气优化利用", 齐鲁石油化工, no. 02, pages 168 - 173 * |
| 袁永瑜;: "优化C2资源增产高附加值产品――我公司建设10万吨/年催化裂化装置干气制乙苯装置可行性预测", 化学工程与装备, no. 05 * |
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